EP2107629A1 - Flexible, hocheffiziente Brennstoffreformierung in einem Festoxidbrennstoffzellensystem - Google Patents

Flexible, hocheffiziente Brennstoffreformierung in einem Festoxidbrennstoffzellensystem Download PDF

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Publication number
EP2107629A1
EP2107629A1 EP09155178A EP09155178A EP2107629A1 EP 2107629 A1 EP2107629 A1 EP 2107629A1 EP 09155178 A EP09155178 A EP 09155178A EP 09155178 A EP09155178 A EP 09155178A EP 2107629 A1 EP2107629 A1 EP 2107629A1
Authority
EP
European Patent Office
Prior art keywords
fuel
reformate
reformer
hydrocarbon
stack
Prior art date
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Granted
Application number
EP09155178A
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English (en)
French (fr)
Other versions
EP2107629B1 (de
Inventor
Christopher M. Mergler
Sean M. Kelly
Gary D. Blake
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Delphi Technologies Inc
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Delphi Technologies Inc
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Publication date
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Publication of EP2107629A1 publication Critical patent/EP2107629A1/de
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Publication of EP2107629B1 publication Critical patent/EP2107629B1/de
Not-in-force legal-status Critical Current
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
    • H01M8/04022—Heating by combustion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0637—Direct internal reforming at the anode of the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to solid oxide fuel cell (SOFC) systems; more particularly, to such systems wherein a portion of the anode tail gas is recirculated directly into the reformer; and most particularly, to a system wherein reformate from a partial-oxidation hydrocarbon reformer, with unprocessed hydrocarbon fuel, is passed through a hydrocarbon cracker ahead of the fuel cell stack to permit internal reforming of small aliphatic residues such as methane within the fuel cell stack.
  • SOFC solid oxide fuel cell
  • SOFC systems are well known.
  • An SOFC typically is fueled by "reformate” gas, which is the partially oxidized effluent from a catalytic partial oxidation (CPOx) hydrocarbon reformer.
  • Reformate typically includes amounts of carbon monoxide (CO) as fuel in addition to molecular hydrogen (H 2 ).
  • CO carbon monoxide
  • H 2 molecular hydrogen
  • the CPOx reactions also release heat that serves to maintain the temperature of the reformer.
  • a CPOx reformer is a very simple and easily controlled device with good transient behavior and dynamic range.
  • a known disadvantage of a CPOx reformer is that it has a relatively low fuel-processing efficiency that limits overall system efficiency.
  • Stack anode tail gas recycle is known to be enhanced by fuel reformer technology that can sustain its temperature in the presence of endothermic reactions.
  • Such technology may consist of a heat exchanger construction wherein hot combustor effluent passes on one side of the heat exchanger (combustor side), and a mix of fuel, air, and recycle gas passes through the other side (reforming side).
  • the reforming side is catalytically treated to allow for the preferred reactions to occur. This mechanization yields high fuel processing efficiencies that, in turn, yield high system efficiencies.
  • an SOFC stack system in accordance with the invention includes an endothermic reformer and fuel flow arrangement that permits optimized fuel reforming at all power load levels of the fuel cell stack between 0% and 100%.
  • a portion of the anode tail gas is recycled into a preparatory mixing chamber wherein the tail gas is combined with fresh air and fuel.
  • the mixture is sent to a main reformer that is configured for endothermic reforming. Reformate from the main reformer, and during higher load operation, unprocessed fuel mixed with reformate, is sent through a hydrocarbon cracker that breaks any hydrocarbons in the reformate into methane before the reformate enters the stack.
  • This invention allows for a reforming strategy that includes the following operation, or any blend thereof.
  • the first mode is at 0% load, and there is no reforming in the stack, all reforming is done in the main reformer.
  • the second mode is at 100% load when all of the fuel is internally reformed by the stack and none of the fuel is reformed in the main reformer.
  • the reforming is a mixture of CPOx and endothermic reforming in the main reformer and internal reforming within the fuel cell stack. This strategy allows the system to take advantage of the highest fuel processing efficiencies available through the full range of stack operation.
  • a first prior art SOFC system 10 comprises an SOFC stack 12 having an anode inlet 14 for reformate 16 from a CPOx reformer 18; an anode tail gas outlet 20; an inlet 22 for heated cathode air 24 from a cathode air heat exchanger 26; and a cathode air outlet 28.
  • Anode tail gas 30 and spent cathode air 32 are fed to a burner 34, the hot exhaust 35 from which is passed through heat exchanger 26 to heat the incoming cathode air 36.
  • the residual potential chemical energy (H 2 and CO) in the anode tail gas is not recovered as additional electrical output 38 of the stack but instead is partially recovered as heat energy in exchanger 26.
  • a second prior art SOFC system 110 comprises the elements just described for first prior art system 10.
  • a first portion 140 of anode tail gas 30 is diverted away from burner 34 to an anode tail gas cooler 142 and thence through an anode tail gas pump 144 which directs cooled portion 141 of the tail gas into an entrance to an air/fuel preparation chamber 148 ahead of endothermic reformer 118.
  • Second portion 143 of anode tail gas 30 is sent to burner 34 as in embodiment 10, and the hot effluent 135 is sent to cathode air heat exchanger 26 via a prior heat exchanger in reformer 118.
  • Fortified reformate 116 is sent to stack anode inlet 14.
  • SOFC system 210 as disclosed in co-pending application Serial No. 11/231,703 is substantially the same as that of prior art embodiment 110 except that anode tail gas 241 from pump 244 is directed via pump 244 to the anode inlet 14 of stack 12, bypassing reformer 18, where the anode tail gas joins with reformate 16 from reformer 18 to form a feed stream 216.
  • the burner effluent 235 bypasses reformer 18.
  • reformer 18 is a CPOx reformer
  • a secondary, independently controlled fuel flow 269 is provided for supplying secondary fuel 270 into anode tail gas portion 240 to optimize the mixture feed stream 216 provided to stack anode inlet 12.
  • the tail gas/secondary fuel mixture is passed through a cleanup catalyst 280 to reduce longer chain hydrocarbons to methane, H 2 , and CO.
  • Primary fuel reformer 18 which is a simple and robust CPOx technology reformer, supplies between 0% and 100% of the reformate to the SOFC stack, with typical values between 30% and 70%. At 100%, there is no secondary fuel injection 270 to the recycle feed stream 216 and no internal reforming in the stack (0% internal reforming). At 0%, there is no CPOx reformate 16 to the stack and all of the secondary fuel 270 from flow control 269 is internally reformed (100% internal reforming).
  • This blended strategy referred to herein as "Light Internal Reforming" generally results in a reformate feed stream 216 to the stack that has a high concentration of H 2 and H 2 O, as well as moderate amounts of CO and CO 2 , and a small amount (0 - 30%) of methane gas (CH 4 ).
  • This arrangement allows for endothermic reforming within the stack itself for high fuel processing efficiencies and high electric output 238. Further, this arrangement allows for reduced internal reforming load ( ⁇ 100%) on the stack which can improve durability.
  • the CPOx reformer primary fuel processing serves the needs of the system during the start-up phase when the stacks are not operational but are warming-up, as well as under transient conditions where less internal reforming may be desirable.
  • a problem with system 210 is that internal reforming is only available at higher electric loads. Thus, system 210 is relatively inefficient under low load conditions. Further, the benefits of passing the anode recycle through the reformer, as in system 110, are not available. Thus, system 210 cannot enjoy use of anode recycle in endothermic reforming at any load condition.
  • a hybrid, flexible SOFC system 310 in accordance with the invention comprises most of the elements just described for second prior art system 110 which need not be repeated here. The following elements, however, are of special interest in system 310.
  • First portion 140 of anode tail gas 30 is diverted ahead of burner 34 to anode tail gas cooler 142 and thence through anode tail gas pump 144 which directs cooled portion 141 into an air/fuel preparation chamber 148 ahead of endothermic reformer 18.
  • Second portion 143 of anode tail gas 30 is sent to burner 34, and the hot effluent 135 is sent to cathode air heat exchanger 26 via a heat exchanger 137 in reformer 18.
  • Fortified reformate 116, including secondary fuel input from 370 is sent to stack anode inlet 14 via a hydrocarbon cracker 360 to ensure that any residual hydrocarbon molecules in reformate 116 are small enough, and preferably are only methane, to be internally reformed within SOFC stack 12.
  • Hydrocarbon cracker 360 may be of any type as are well known in the art for breaking long-chain aliphatic compounds into short-chain aliphatic compounds.
  • reformate 316 entering stack 12 has high concentrations of H 2 and H 2 O, moderate amounts of CO and CO 2 , and a small amount of methane gas (CH 4 ); whereas, under relatively high stack load conditions, reformate 316 entering stack 12 has a high concentration of H 2 O, relatively little H 2 and CO, and a large amount of methane gas (CH 4 ).
  • Reformer 18 may be fueled by a wide range of hydrocarbon fuels including but not limited to gasoline, JP-8, diesel, LPG, and natural gas. Further, the addition of hydrocarbon cracker 360 permits operation of stack 12 at any ratio of endothermic reforming to internal reforming between 100% endothermic and 100% internal, depending upon load 138.
  • controller 362 senses demanded load 138 and commands actuators 364 that control at least air flow 366 and fuel flows 368,370 with programmed responses to provide the optimal endothermic/internal reforming ratio.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Fuel Cell (AREA)
  • Hydrogen, Water And Hydrids (AREA)
EP09155178A 2008-04-04 2009-03-13 Flexible, hocheffiziente Brennstoffreformierung in einem Festoxidbrennstoffzellensystem Not-in-force EP2107629B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US12/080,589 US7901820B2 (en) 2005-09-21 2008-04-04 Solid oxide fuel cell stack assembly and method for fueling

Publications (2)

Publication Number Publication Date
EP2107629A1 true EP2107629A1 (de) 2009-10-07
EP2107629B1 EP2107629B1 (de) 2011-11-16

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EP09155178A Not-in-force EP2107629B1 (de) 2008-04-04 2009-03-13 Flexible, hocheffiziente Brennstoffreformierung in einem Festoxidbrennstoffzellensystem

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US (1) US7901820B2 (de)
EP (1) EP2107629B1 (de)
AT (1) ATE534161T1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT508594A1 (de) * 2009-07-16 2011-02-15 Avl List Gmbh Verfahren zum betrieb einer hochtemperatur-brennstoffzelle
US8440358B2 (en) * 2011-12-09 2013-05-14 Delphi Technologies, Inc. Method of operating a fuel cell system on low quality by-product gases
US10381669B2 (en) * 2016-07-13 2019-08-13 Lg Fuel Cell Systems Inc. Steam reformer for in-block fuel cell reforming

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4642272A (en) * 1985-12-23 1987-02-10 International Fuel Cells Corporation Integrated fuel cell and fuel conversion apparatus
US20020031690A1 (en) * 2000-09-13 2002-03-14 Toyota Jidosha Kabushiki Kaisha Fuel reforming apparatus
US20040006914A1 (en) * 2002-07-10 2004-01-15 Shaaban Aly H. Compact distillates fuel processor with effective sulfur removal process
US20040224196A1 (en) * 2003-05-06 2004-11-11 Michael Pastula Thermally integrated sofc system
US20070065687A1 (en) 2005-09-21 2007-03-22 Kelly Sean M Method and apparatus for light internal reforming in a solid oxide fuel cell system
US20070160880A1 (en) * 2006-01-09 2007-07-12 Fischer Bernhard A Fuel-staged hydrocarbon reformer system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4642272A (en) * 1985-12-23 1987-02-10 International Fuel Cells Corporation Integrated fuel cell and fuel conversion apparatus
US20020031690A1 (en) * 2000-09-13 2002-03-14 Toyota Jidosha Kabushiki Kaisha Fuel reforming apparatus
US20040006914A1 (en) * 2002-07-10 2004-01-15 Shaaban Aly H. Compact distillates fuel processor with effective sulfur removal process
US20040224196A1 (en) * 2003-05-06 2004-11-11 Michael Pastula Thermally integrated sofc system
US20070065687A1 (en) 2005-09-21 2007-03-22 Kelly Sean M Method and apparatus for light internal reforming in a solid oxide fuel cell system
US20070160880A1 (en) * 2006-01-09 2007-07-12 Fischer Bernhard A Fuel-staged hydrocarbon reformer system

Also Published As

Publication number Publication date
US7901820B2 (en) 2011-03-08
ATE534161T1 (de) 2011-12-15
US20080187799A1 (en) 2008-08-07
EP2107629B1 (de) 2011-11-16

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